Plastic oxy-aromatic petroleum wax and method of making the same



Patented May 1946 AND METHOD OF MAKING THE SAME Orland M. new and John D. zeta, Woodbury, N. J., assignors to Socony-Vacuum Oil Company, Incorporated, New

York, N. Y., a corporation of New York No Drawing. Application February 25,1942,

' 7 Serial N0. 432,278

Claims. (01. 260 -61) 0 This invention relates to plastic compositions of matter and a method for making the same and is particularly concerned with a process including alkylation of aromatics with long chain aliphatic groups, causing the aliphatic groups to contain halogen substituents, and dehalogenating. The invention also comprises the improved compositions of matter so prepared.

In general, the first step of the process, alkylation, is preferably conducted inaccordance with the disclosures in application Serial Number 427,588, filed January 21, 1942, by 0. M. Reiii and J. J. Giammaria; and application Serial Number 423,580, filed December 9, 1941, by F. P. Otto and O. M. Rein, issued February 1, 1944 as Patent No. 2,340,838. The said disclosures relate to condensation of aromatics with chlorinated aliphatlcs in the presence or Friedel-Craits cat alysts. The products of the first of said applications are plastic and rubber-like compositions resulting from reaction of chlorinated waxes of at least chlorine content with aromatic material in proportions to polyalkylate the aromatics; while those of the latter application are 7 hard resinous bodies produced by reaction of chlorinated aliphatics having more than 10 carbon atoms and containing from to chlorine with aromatic material in proportions such that there is present at least one mol oi aromatic for each atomic weight 01 chlorine in the chlorinated aliphatic. By applying the principles oi this invention to either or those compositions, theproperties thereof. may be extensively modified, rendering them more suitable for many of the purposes to which they are adapted and modifying their characteristics to adapt them to further uses.

The invention is not limited tocompositions of the type described in the two said applications, however, but may be utilized in connection with any plastic body wherein the characterizing component 'is an alkaryl or aralkyl composition. It

7 will beseen as the description of the invention develops that superior results are obtained with certain plastic and rubber-like compositions described in the said application oi Rail! and Glammarla because of the greater toughness and elasticity imparted thereto by the present process. Other plastic compositions of the types set out above are modified vsimilarly to give greater tol shness and/or tensile strength or advantaseous changes in related properties.

In preparation oi the alkyiated aromatic compound, molecular weight and degree of chlorine.- tlon oi the aliphatic to be substituted on the arcmatie nuclei, are of primary importance. The degree of substitution, governed by the relative molecular ratios of aromatic compounds to combined chlorine are to be considered as governing to a. large extent the properties of compositions within the scope oi the invention. The aliphatic compounds used for alkylation are preferably derived from petroleum or other mineral wax, although other waxes and aliphatic compounds having a fairly high molecular weight may be employed. Stoddard solvent, ior example, may be chlorinated and reacted with an aromatic to produce a suitable composition. In general, the aliphatic material used, usually a mixture of several aliphatic compounds, should be composed primarily 0! a compound or. compounds having at least 10 carbon atoms. Better results are usually obtained by using petroleum waxes which average about 24 carbon atoms per molecule and, have few, if any, components below 20 carbon atoms per molecule, although compounds having as few as 15 carbon atoms have been res more resinous character, whilethe poly-alky1at-- ed materials are more resilient. In general, the

ported as being present in typical petroleum waxes.

terial is a factor controlling hardness and/or resiliency of the finished product, the hardness increasing and the resiliency decreasing as the degree of chlorination is increased. The degree of substitution also aii'ects these and other properties; Mono-alkylated aromatics usually. show a oxyaromatic compounds, such as phenol, the naphthols and diphenyl ether, produce 'moreelastic products than the aromatic hydrocarbons, and other derivatives of men-cyclic, or poly-cyclic aromatics. Having reacted the chlorinated aliphatic'and the aromatic material, asby a Friedel- Crafts reaction between the aromatic and chlorinated aliphatic reactants, the product oi that reaction is further treated by dehalogenation.

Although products of this type generally contain some chlorine because 01 incomplete reaction, the amount 01' chlorine remaining will usually not exceed about two per cent by weight. In order to form a wax aromatic compound, particularly of the wax phenol type. completely free of chlorine, it is necessary to run-a prolonged reaction which results in some cracking of the substituted wax groups and the formation or a proda cs.

According to the present invention, a higher amount of halogen is intentionally allowed to re- The degree of chlorination of the aliphatic ma- 4 not at lower viscosity and or less desirable char- PREPARATION or PLAsTIc AND RUBBER-Lin COMPOSITIONS In the following examples, procedures will be given for the formation of the halogen-containing wax aromatic compounds as division (a) and the dehalogenation step will be outlined as part (b) (a) Halogen-containing war aromatic compounds A rubber-like composition comprising a chicrine-containing wax phenol, prepared as outlined below, by trisubstitution of phenol with .wax of 25% chlorine content, will have a phenol content of about 25%, a chlorine content of about 5%, the remainder of the molecule consisting of combined wax. The compositions may be represented by the following general formula which is not an attempt to give, however, an exact representation of the molecule. For simplicity, the different aromatic nuclei are represented by the phenyl radical.

The compositions are represented in the foregoing formula with a single attachment of the aromatic. group to each wax group, but in the reaction of chlorwax of high chlorine content with aromatic compound as carried out in the preparation of plastic and rubber-like compositions, apparently the aromatic group will be attached in some cases to more than one carbon of the same wax group, particularly in reactions with aromatic compounds of the condensed nuclei and polycyclic type.

Some chain formation would be expected to occur in the reaction of aromatic compounds with chlorinated waxes, in which case the following representation would be applicable, representing a continuation of the chain structure:

The halogen is represented in the foregoing formulae a an end carbon substituent, but the position of the halogen group is undeterminable, except that it is substituted in the aliphatic group. The compositions are represented as dialkylesubstituted aromatic compounds, but an amount of chlorwax can bereacted which is sufficient to substitute all th re a able hydrogen dry.

of the aromatic nuclei. Generally, an amount of chlorwax ufiicient to at least tri-substitute the aromatic compound is favored. Chlorinated wax of 50% chlorine content can be prepared conveniently. This degree of chlorination of the wax can be used in formation of the plastic and rubber-like compositions, but will require the use of a powerful mixer because of the high viscosity of the mixture obtained. A tough, rubber-like product results during the formation of the wax phenol, described below, containing 5% chlorine, which can becarried out in ordinary laboratory reactors of glass.

EXAMPLE I PREPARATION or WAx PHENOL CONTAINING CHLORINE Reaction mixture:

Grams Phenol 44 Chlorinated wax of -25% chlorine content 200 AlCla (anhy.) 3 Parafiin wax of ASTM melting point of about 126 F. and of average molecular weight of about 350 is melted and acurrent of chlorine is introduced'at a temperature of about 250 F. until 25% by weight of chlorine is absorbed. The phenol is then added, followed by addition of the anhydrous AlCla at a temperature of about F. with rapid stirring. The temperature of the mixture is gradually raised to about 350 F. during a one-hour period with efilcient stirring to reduce foaming caused by evolution of HCl. The reaction mixture is then held at this temperature about one hour to bring about suiflcient reaction.

It has been disovered that the reaction product upon becoming highly viscous and difiicult to stir will break up into fine particles if allowed to stand with the temperature maintained at the point of high viscosity development. Hence it iscustomary to discontinue stirring at the point of high viscosity, followed by renewed stirring at the point where break up of the material occurs.

High viscosity development in the formation of the present wax phenol occurs at about 325 F.

The reaction mixture is then cooled and contacted with water to decompose the aluminum chloride reaction product, whereby the aluminum chloride can be removed from the mixture. To ensure complete removal of any corrosive halogen, the'product is digested wtih dilute (1%.) caustic soda by refluxing the mixture several hours, followed by removing the alkaline solution and water washing or neutralizing with dilute hydrochloric or acetic acid. Aqueous ammonia can also be used in the removal of corrosive halogen, which is advantageous because of the readiness with which the ammonia can be removed after the digesting operation. During this purification, the product becomes coagulated and in this state can be formed into a sheet by running through squeeze rolls and further washing with water in this rolling operation. The rubber-like composition can be readily dried on a heated mill roll or can-be cut into sheets and laid aside to In the foregoing procedure, the chlorine content of the finished product is controlled by the amount of A1012 used as catalyst in the Friedel- Crafts reaction. As an alternative Procedure, the chlorwax and phenol can be reacted in the presence of sufiicient AlCls to substantially eliminate the chlorine as HCl, followed by coo ing the mixture, diluting with ethylene dichloride and introducing chlorine until the desired.

amount of halogen is absorbed. The reaction product is then purified as outlined above. This procedure is only applicable where the wax phenol is soluble in organic solvents, as for example, a diwax phenol prepared from wax 01' 27% chlorine content.

(by Dehalogenation oj'halogen-containing was:

aromatic compounds .Contact clays and silica gel are excellent dehalogenating agents, but their removal from the plastic and rubber-like compositions is difiicult.

When the dehalogenation is carried out in the presence of caustic soda, some hydroxylation takes place; in the presence of ammonia or amines, amino groups are introduced; in the presence of alkali cyanides, cyanates, or thincyanates, cyano, cyanate and thio-cyanate groups, respectively, are introduced. Any method of dehalogenation, however, results in the formation of unsaturated products. Dehalogenatlon in the presence of dilute caustic soda for the purpose of neutralizing HCl is the preferred procedure.

DanALocsNArroN or Wax PHENOL CONTAINING 4% CHLoaINn Reaction mixture:

Wax phenol (prepared as in (a) above) grams- 260 3% Caustic soda solution cc 700 Procedure The chlorine-containing wax phenol from the Friedel-Crafts reactor is agitated with the dilute caustic soda solution at a temperature of about 500 F. for a period of about 4 hours. In the dehalogenation, the product is broken up into small particles which can be readily purified by water complete neutralization of any corrosive HCl.

The product is then further washed with water and milled into sheets by the procedure outlined above in the purification ofv the chlorine-containing wax aromatic compounds. 1

The more resinous or harderplastic compositions which can be formed from wax aromatic compounds such as diwax phenol from wax or a 35% chlorine content, are also produced according to the foregoing procedure. Thefinished product, however, cannot be rolled into sheet form by milling operations and is handled in the form or a powder or small particle size for use as a molding composition. These products can be molded to give tough, resilient compositions of high Iusion point without the aid of. resinifylng gen will remain because oi incomplete dehaio genation. A minor amount or hydroxylation will be obtained since caustic soda is used as the dehalogenating agent.

When a hard plastic is formed byv reaction of an aromatic compound with a chiorwax of higher chlorinecontent than the above, a product of higher aromatic content is formed. Diwax phenol from wax of 35% chlorine", for instance, con taining 7.36% chlorine is converted into a hardplastic composition when 'dehalogenated, having a phenol content or about 42% and a combined wax content of about 58%.

EXAMPLE II 1 Using the procedure for forming wax-substituted aromatic compounds as outlined in the foregoing example of the formation of wax phenol containing chlorine, 400 grams of chlorinated wax or 25% chlorine content are reacted with 53 grams of diphenylether in the presence of 5 grams of anhydrous .AlCla as catalyst to form an elastic composition.

This product is then dehalogenated accordin to Example I-(b) to form arubber-like composition of improved tensile strength. -A product or this kind has a combined diphenyl ether content of about 15% and approximately of combined wax.

EXAIVIPLE 111 Following the above procedure, 488 grams or chlorinated wax containing 55% chlorine are reacted with 198 grams of diphenyl to form a waxsubstituted compound having a chlorine content of about 25%. When dehalogenated by reaction with an aqueous solution of caustic soda at 500 F. during a 2-hour period, a hard resinous composition is formed which can be molded under pressure to give tough products having high resistance to shock. A resin formed in this manner will have a chlorine content of about 8%.

It will be clear. or. course, that unsaturation 'oi the halogen-containing alkylated aromatic compounds will result in some modification of properties. there should be removal of at least about 2% of halogen based on weight of the halogenated composition; while preferred compositions are prepared by removal of at least 5% by weight of halogen. The halogen may, as noted above, be caused to be present in the intermediate composition either by halogenating alter the Friedel-Craits reaction or by conducting that reaction in such manner as to result in residual halogen being present.

The preferred products, obtained by dehalogenation oi. a halogenated composition resulting from the reaction or aromatics with halogenated aliphatic compounds oi at least 20 carbon atomsand containing at least 25% of halogen in proportions to polyalkylate, is admirably suited to uses to which rubber is put and vulcanizes very well: either alone or in combination with natural rubber.

We claim:

1. The-process which comprises efiecting iormation of aplastic body containing combined halogen by heating chlorinated petroleum we: of at least 25% chlorine content with an oxy-aro- ,matic material selected i'rom the group consisting of phenol, the naphthols, and diphenyl ether in the presence of a Friedel-Crafts catalyst and In order to obtain marked modification,

the. combined chlorine removed from said body being at least 2% by weight.

I 2. The process which comprises eiiecting formation of a plastic body containing combined halogen by heating chlorinated petroleum wax of at least 25% chlorine content with phenol in the presence of aFriedel-Crafts catalyst and in a proportion of chlorinated wax to phenol such as to theoretically result in polyalkylation of the phenol, and thereafter dechlorinating said body by heating the same with a dilute aqueous caustic solution; the combined chlorine removed from said body being at least 2% by weight.

3. The process which comprises effecting formation of a plastic body containing combined halogen by heating chlorinated petroleum wax of at least 25% chlorine content with phenol in the presence of a Friedel-Crafts catalyst and thereafter dechlorinating said body by heating the same with a dilute aqueous caustic solution.

4. A composition of matter comprising a-plastic halogen by heating chlorinated petroleum wax of at least 25% chlorine content with an oxyaromatic' material selected from the group consisting of phenol, the naphthols, and diphenyl ether in the presence of a Friedel-Cratts catalyst,

and thereafter dechlorinating said body by heating the same with a dilute aqueous caustic solution.

ORLAND M. REIFF. JOHN D. ZECH. 

